Process and apparatus for obtaining bulk monocrystalline gallium-containing nitride

ABSTRACT

The present invention refers to an ammonobasic method for preparing a gallium-containing nitride crystal, in which gallium-containing feedstock is crystallized on at least one crystallization seed in the presence of an alkali metal-containing component in a supercritical nitrogen-containing solvent. The method can provide monocrystalline gallium-containing nitride crystals having a very high quality.

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] The present invention refers to processes for obtaining a gallium-containing nitride crystal by an ammonobasic method as well as the gallium-containing nitride crystal itself. Furthermore, an apparatus for conducting the various methods is disclosed.

[0003] 2. Discussion of the Related Art

[0004] Optoelectronic devices based on nitrides are usually manufactured on sapphire or silicon carbide substrates that differ from the deposited nitride layers (so-called heteroepitaxy). In the most often used Metallo-Organic Chemical Vapor Deposition (MOCVD) method, the deposition of GaN is performed from ammonia and organometallic compounds in the gas phase, and the growth rates achieved make it impossible to provide a bulk layer. The application of a buffer layer reduces the dislocation density, but not more than to approx. 10⁸/cm². Another method has also been proposed for obtaining bulk monocrystalline gallium nitride. This method consists of an epitaxial deposition employing halides in a vapor phase and is called Halide Vapor Phase Epitaxy (HVPE) [“Optical patterning of GaN films” M. K. Kelly, O. Ambacher, Appl. Phys. Lett. 69 (12) (1996) and “Fabrication of thin-film InGaN light-emitting diode membranes” W. S. Wrong, T. Sands, Appl. Phys. Lett. 75 (10) (1999)]. This method allows for the preparation of GaN substrates having a 2-inch diameter.

[0005] However, their quality is not sufficient for laser diodes, because the dislocation density continues to be approx. 10⁷ to approx. 10⁹/cm². Recently, the method of Epitaxial Lateral Overgrowth (ELOG) has been used for reducing the dislocation density. In this method the GaN layer is first grown on a sapphire substrate and then a layer with SiO₂ is deposited on it in the form of strips or a lattice. On the thus prepared substrate, in turn, the lateral growth of GaN may be carried out leading to a dislocation density of approx. 10⁷/cm².

[0006] The growth of bulk crystals of gallium nitride and other metals of group XIII (IUPAC, 1989) is extremely difficult. Standard methods of crystallization from melt and sublimation methods are not applicable because of the decomposition of the nitrides into metals and N₂. In the High Nitrogen Pressure (HNP) method [“Prospects for high-pressure crystal growth of III-V nitrides” S. Porowski et al., Inst. Phys. Conf. Series, 137, 369 (1998)] this decomposition is inhibited by the use of nitrogen under the high pressure. The growth of crystals is carried out in molten gallium, i.e. in the liquid phase, resulting in the production of GaN platelets about 10 mm in size. Sufficient solubility of nitrogen in gallium requires temperatures of about 1500° C. and nitrogen pressures in the order of 15 kbar.

[0007] The use of supercritical ammonia has been proposed to lower the temperature and decrease the pressure during the growth process of nitrides. Peters has described the ammonothermal synthesis of aluminium nitride [J. Cryst. Growth 104, 411-418 (1990)]. R. Dwilinski et al. have shown, in particular, that it is possible to obtain a fine-crystalline gallium nitride by a synthesis from gallium and ammonia, provided that the latter contains alkali metal amides (KNH₂ or LiNH₂) . The processes were conducted at temperatures of up to 550° C. and under a pressure of 5 kbar, yielding crystals about 5 μm in size [“AMMONO method of BN, AlN, and GaN synthesis and crystal growth”, Proc. EGW-3, Warsaw, Jun. 22-24, 1998, MRS Internet Journal of Nitride Semiconductor Research, http://nsr.mij.mrs.org/3/25]. Another supercritical ammonia method, where a fine-crystalline GaN is used as a feedstock together with a mineralizer consisting of an amide (KNH₂) and a halide (KI) also provided for recrystallization of gallium nitride [“Crystal growth of gallium nitride in supercritical ammonia” J. W. Kolis et al., J. Cryst. Growth 222, 431-434 (2001)]. The recrystallization process conducted at 400° C. and 3.4 kbar resulted in GaN crystals about 0.5 mm in size. A similar method has also been described in Mat. Res. Soc. Symp. Proc. Vol. 495, 367-372 (1998) by J. W. Kolis et al. However, using these supercritical ammonia processes, no production of bulk monocrystalline was achieved because no chemical transport processes were observed in the supercritical solution, in particular no growth on seeds was conducted.

SUMMARY OF THE INVENTION

[0008] Therefore, it is an object of the present invention to provide an improved method of preparing a gallium-containing nitride crystal.

[0009] The lifetime of optical semiconductor devices depends primarily on the crystalline quality of the optically active layers, and especially on the surface dislocation density. In case of GaN based laser diodes, it is beneficial to lower the dislocation density in the GaN substrate layer to less than 10⁶/cm², and this has been extremely difficult to achieve using the methods known so far. Therefore, a further object of the invention is to provide gallium-containing nitride crystals having a quality suitable for use as substrates for optoelectronics.

[0010] The above objects are achieved by the subject matter recited in the appended claims. In particular, in one embodiment the present invention refers to a process for obtaining a gallium-containing nitride crystal, comprising the steps of:

[0011] providing a gallium-containing feedstock, an alkali metal-containing component, at least one crystallization seed and a nitrogen-containing solvent in at least one container;

[0012] bringing the nitrogen-containing solvent into a supercritical state;

[0013] (iii) at least partially dissolving the gallium-containing feedstock at a first temperature and at a first pressure; and

[0014] (iv) crystallizing gallium-containing nitride on the crystallization seed at a second temperature and at a second pressure while the nitrogen-containing solvent is in the supercritical state;

[0015] wherein at least one of the following criteria is fulfilled:

[0016] (a) the second temperature is higher than the first temperature; and

[0017] (b) the second pressure is lower than the first pressure.

[0018] In a second embodiment a process for preparing a gallium-containing nitride crystal is described which comprises the steps of:

[0019] (i) providing a gallium-containing feedstock comprising at least two different components, an alkali metal-containing component, at least one crystallization seed and a nitrogen-containing solvent in a container having a dissolution zone and a crystallization zone, whereby the gallium-containing feedstock is provided in the dissolution zone and the at least one crystallization seed is provided in the crystallization zone;

[0020] (ii) subsequently bringing the nitrogen-containing solvent into a supercritical state;

[0021] (iii) subsequently partially dissolving the gallium-containing feedstock at a dissolution temperature and at a dissolution pressure in the dissolution zone, whereby a first component of the gallium-containing feedstock is substantially completely dissolved and a second component of the gallium-containing feedstock as well as the crystallization seed remain substantially undissolved so that an undersaturated solution with respect to gallium-containing nitride is obtained;

[0022] (iv) subsequently setting the conditions in the crystallization zone at a second temperature and at a second pressure so that over-saturation with respect to gallium-containing nitride is obtained and crystallization of gallium-containing nitride occurs on the at least one crystallization seed and simultaneously setting the conditions in the dissolution zone at a first temperature and at a first pressure so that the second component of the gallium-containing feedstock is dissolved;

[0023] wherein the second temperature is higher than the first temperature.

[0024] A gallium-containing nitride crystal obtainable by one of these processes is also described. Further subject matter of the invention are a gallium-containing nitride crystal having a surface area of more than 2 cm² and having a dislocation density of less than 10⁶/cm² and a gallium-containing nitride crystal having a thickness of at least 200 μm and a full width at half maximum (FWHM) of X-ray rocking curve from (0002) plane of 50 arcsec or less.

[0025] The invention also provides an apparatus for obtaining a gallium-containing nitride crystal comprising an autoclave (1) having an internal space and comprising at least one device (4, 5, 6) for heating the autoclave to at least two zones having different temperatures, wherein the autoclave comprises a device which separates the internal space into a dissolution zone (13) and a crystallization zone (14).

[0026] In a yet another embodiment, a process for preparing a bulk monocrystalline gallium-containing nitride in an autoclave is disclosed, which comprises the steps of providing a supercritical ammonia solution containing gallium-containing nitride with ions of alkali metals, and recrystallizing said gallium-containing nitride selectively on a crystallization seed from said supercritical ammonia solution by means of the negative temperature coefficient of solubility and/or by means of the positive pressure coefficient of solubility.

[0027] A process for controlling recrystallization of a gallium-containing nitride in a supercritical ammonia solution which comprises steps of providing a supercritical ammonia solution containing a gallium-containing nitride as a gallium complex with ions of alkali metal and NH₃ solvent in an autoclave and decreasing the solubility of said gallium-containing nitride in the supercritical ammonia solution at a temperature less than that of dissolving gallium-containing nitride crystal and/or at a pressure higher than that of dissolving gallium-containing nitride crystal is also disclosed.

BRIEF DESCRIPTION OF THE DRAWINGS

[0028]FIG. 1 shows the dependency of the solubility of gallium-containing nitride in supercritical ammonia that contains potassium amide (with KNH₂:NH₃=0.07) on pressure at T=400° C. and T=500° C.

[0029]FIG. 2 shows the diagram of time variations of temperature in an autoclave at constant pressure for Example 1.

[0030]FIG. 3 shows the diagram of time variations of pressure in an autoclave at constant temperature for Example 2.

[0031]FIG. 4 shows the diagram of time variations of temperature in an autoclave at constant volume for Example 3.

[0032]FIG. 5 shows the diagram of time variations of temperature in an autoclave for Example 4.

[0033]FIG. 6 shows the diagram of time variations of temperature in an autoclave for Example 5.

[0034]FIG. 7 shows the diagram of time variations of temperature in an autoclave for Example 6.

[0035]FIG. 8 shows the diagram of time variations of temperature in an autoclave for Example 7.

[0036]FIG. 9 shows a schematic axial cross section of an autoclave as employed in many of the examples, mounted in the furnace.

[0037]FIG. 10 is a schematic perspective drawing of an apparatus according to the present invention.

[0038]FIG. 11 shows the diagram of time variations of temperature in an autoclave at constant volume for Example 8.

[0039]FIG. 12 shows the diagram of time variations of temperature in an autoclave at constant volume for Example 9.

[0040]FIG. 13 shows the diagram of time variations of temperature in an autoclave at constant volume for Example 10.

[0041]FIG. 14 shows the diagram of time variations of temperature in an autoclave at constant volume for Examples 11 and 12.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0042] In the present invention the following definitions apply.

[0043] Gallium-containing nitride means a nitride of gallium and optionally other element(s) of group XIII (according to IUPAC, 1989). It includes, but is not restricted to, the binary compound GaN, ternary compounds such as AlGaN, InGaN and also AlInGaN, where the ratio of the other elements of group XIII to Ga can vary in a wide range.

[0044] Bulk monocrystalline gallium-containing nitride means a monocrystalline substrate made of gallium-containing nitride from which optoelectronic devices such as LED or LD can be formed by epitaxial methods such as MOCVD and HVPE.

[0045] Supercritical solvent means a fluid in a supercritical state. It can also contain other components in addition to the solvent itself as long as these components do not substantially influence or disturb function of supercritical solvent. In particular, the solvent can contain ions of alkali metals.

[0046] Supercritical solution is used when referring to the supercritical solvent when it contains gallium in a soluble form originating from the dissolution of gallium-containing feedstock.

[0047] Dissolution of gallium-containing feedstock means a process (either reversible or irreversible) in which said feedstock is taken up to the supercritical solvent as gallium in a soluble form, possibly gallium-complex compounds.

[0048] Gallium-complex compounds are complex compounds, in which a gallium atom is a coordination center surrounded by ligands, such as NH₃ molecules or its derivatives, like NH₂ ⁻, NH²⁻, etc.

[0049] Negative temperature coefficient of solubility means that the solubility of the respective compound is a monotonically decreasing function of temperature if all other parameters are kept constant. Similarly, positive pressure coefficient of solubility means that, if all other parameters are kept constant, the solubility is a monotonically increasing function of pressure. In our research we showed that the solubility of gallium-containing nitride in supercritical nitrogen-containing solvents, such as ammonia, possesses a negative temperature coefficient and a positive pressure coefficient in temperatures ranging at least from 300 to 600° C. and pressures from 1 to 5.5 kbar.

[0050] Over-saturation of supercritical solution with respect to gallium-containing nitride means that the concentration of gallium in a soluble form in said solution is higher than that in equilibrium (i.e. it is higher than solubility). In the case of dissolution of gallium-containing nitride in a closed system, such an over-saturation can be achieved by either increasing the temperature and/or decreasing the pressure.

[0051] Spontaneous crystallization means an undesired process where nucleation and growth of the gallium-containing nitride from over-saturated supercritical solution take place at any site within an autoclave except at the surface of a seed crystal where the growth is desired. Spontaneous crystallization also comprises nucleation and disoriented growth on the surface of seed crystal.

[0052] Selective crystallization on a seed means a process of crystallization on a seed carried out without spontaneous crystallization.

[0053] Autoclave means a closed container which has a reaction chamber where the ammonobasic process according to the present invention is carried out.

[0054] The present invention can provide a gallium-containing nitride monocrystal having a large size and a high quality. Such gallium-containing nitride crystals can have a surface area of more than 2 cm² and a dislocation density of less than 10⁶/cm². Gallium-containing nitride crystals having a thickness of at least 200 μm (preferably at least 500 μm) and a FWHM of 50 arcsec or less can also be obtained. Depending on the crystallization conditions, it possible to obtain gallium-containing nitride crystals having a volume of more than 0.05 cm³, preferably more than 0.1 cm³ using the processes of the invention.

[0055] As was explained above, the gallium-containing nitride crystal is a crystal of nitride of gallium and optionally other element(s) of Group XIII (the numbering of the Groups is given according to the IUPAC convention of 1989 throughout this application). These compounds can be represented by the formula Al_(x)Ga_(1-x-y)In_(y)N, wherein 0≦x<1, 0≦y<1, 0≦x+y<1; preferably 0 x<0.5 and 0 y<0.5. Although in a preferred embodiment, the gallium-containing nitride is gallium nitride, in a further preferred embodiment part (e.g. up to 50 mol.-%) of the gallium atoms can be replaced by one or more other elements of Group XIII (especially Al and/or In).

[0056] The gallium-containing nitride may additionally include at least one donor and/or at least one acceptor and/or at least one magnetic dopant to alter the optical, electrical and magnetic properties of the substrate. Donor dopants, acceptor dopants and magnetic dopants are well-known in the art and can be selected according to the desired properties of the substrate. Preferably the donor dopants are selected from the group consisting of Si and O. As acceptor donors Mg and Zn are preferred. Any known magnetic dopant can be included into the substrates of the present invention. A preferred magnetic dopant is Mn and possibly also Ni and Cr. The concentrations of the dopants are well-known in the art and depend on the desired end application of the nitride. Typically the concentrations of these dopants are ranging from 10¹⁷ to 10²¹/cm³.

[0057] Due to the production process the gallium-containing nitride crystal can also contain alkali elements, usually in an amount of more than about 0.1 ppm. Generally it is desired to keep the alkali elements content lower than 10 ppm, although it is difficult to specify what concentration of alkali metals in gallium-containing nitride has a disadvantageous influence on its properties.

[0058] It is also possible that halogens are present in the gallium-containing nitride. The halogens can be introduced either intentionally (as a component of the mineralizer) or unintentionally (from impurities of the mineralizer or the feedstock). It is usually desired to keep the halogen content of the gallium-containing nitride crystal in the range of about 0.1 ppm or less.

[0059] The process of the invention is a supercritical crystallization process, which includes at least two steps: a dissolution step at a first temperature and at a first pressure and a crystallization step at a second temperature and at a second pressure. Since generally high pressures and/or high temperatures are involved, the process according to the invention is preferably conducted in an autoclave. The two steps (i.e. the dissolution step and the crystallization step) can either be conducted separately or can be conducted at least partially simultaneously in the same reactor.

[0060] For conducting the two steps separately the process can be conducted in one reactor but the dissolution step is conducted before the crystallization step. In this embodiment the reactor can have the conventional construction of one single chamber. The process of the invention in the two-step embodiment can be conducted using constant pressure and two different temperatures or using constant temperature and two different pressures. It is also possible to use two different pressures and two different temperatures. The exact values of pressure and temperature should be selected depending on the feedstock, the specific nitride to be prepared and the solvent. Generally the pressure is in the range of 1 to 10 kbar, preferably 1 to 5.5 and more preferably 1.5 to 3 kbar. The temperature is in the range of 100° C. to 800° C., preferably 300° C. to 600° C., more preferably 400° C. to 550° C. If two different pressures are employed, the difference in pressure should be from 0.1 kbar to 9 kbar, preferably from 0.2 kbar to 3 kbar. However, if the dissolution and crystallization are controlled by the temperature, the difference in temperature should be at least 1° C., and preferably from 5° C. to 150° C.

[0061] In a preferred embodiment, the dissolution step and the crystallization step are conducted at least partially simultaneously in the same container. For such an embodiment the pressure is practically uniform within the container, while the temperature difference between the dissolution zone and crystallization zone should be at least 1° C., and preferably is from 5° C. to 150° C. Furthermore, the temperature difference between the dissolution zone and crystallization zone should be controlled so as to ensure chemical transport in the supercritical solution, which takes place through convection.

[0062] A possible construction of a preferred container is given in FIG. 9. For conciseness and ease of understanding in the following, the process will be explained particularly with respect to this preferred embodiment. However, the invention can be conducted with different container constructions as long as the principles outlined in the specification and the claims are adhered to.

[0063] In a preferred embodiment of the invention, the process can be conducted in an apparatus comprising an autoclave 1 having an internal space and comprising at least one device 4, 5, 6 for heating the autoclave to at least two zones having different temperatures, wherein the autoclave comprises a device which separates the internal space into a dissolution zone 13 and a crystallization zone 14. These two zones having different temperatures should preferably coincide with the dissolution zone 13 and the crystallization zone 14. The device which separates the internal space of the autoclave can be, for example, at least one baffle 12 having at least one opening 2. Examples are baffles having a central opening, circumferential openings or a combination thereof. The size of the opening(s) 2 should be large enough to allow transport between the zones but should be sufficiently small to maintain a temperature gradient in the reactor. The appropriate size of the opening depends on the size and the construction of the reactor and can be easily determined by a person skilled in the art.

[0064] In one embodiment, two different heating devices can be employed, the position of which corresponds to dissolution zone 13 and the crystallization zone 14. However, it has been observed that transport of gallium in a soluble form from the dissolution zone 13 to the crystallization zone 14 can be further improved if a third cooling means 6 is present between the first and the second heating devices and is located at approximately the position of the separating device. The cooling means 6 can be realized by liquid (e.g. water) cooling or preferably by fan cooling. The heating devices are powered electrically, by either inductive or, preferably, resistive heating means. Use of a heating 4—cooling 6—heating 5 configuration gives wider possibilities in forming the desired temperature distribution within the autoclave. For example, it enables to obtain low temperature gradients in most of the crystallization zone 14 and of the dissolution zone 13, and a high temperature gradient in the region of baffle 12.

[0065] When the process of the present invention is conducted, providing a gallium-containing feedstock, an alkali metal-containing component, at least one crystallization seed and a nitrogen-containing solvent are provided in at least one container. In the preferred apparatus described above, the gallium-containing feedstock is placed in the dissolution zone and the at least one crystallization seed is placed in the crystallization zone. The alkali metal containing component is also preferably placed in the dissolution zone. Then the nitrogen-containing solvent is added into the container, which is then closed. Subsequently the nitrogen-containing solvent is brought into a supercritical state, e.g. by pressure and/or heat.

[0066] In the present invention any materials containing gallium, which are soluble in the supercritical solvent under the conditions of the present invention, can be used as a gallium-containing feedstock. Typically the gallium-containing feedstock will be a substance or mixture of substances, which contains at least gallium, and optionally alkali metals, other Group XIII elements, nitrogen, and/or hydrogen, such as metallic Ga, alloys and inter-metallic compounds, hydrides, amides, imides, amidoimides, azides. Suitable gallium-containing feedstocks can be selected from the group consisting of gallium nitride GaN, azides such as Ga(N₃)₃, imides such as Ga₂(NH)₃, amido-imides such as Ga(NH)NH₂, amides such as Ga(NH₂)₃, hydrides such as GaH₃, gallium-containing alloys, metallic gallium and mixtures thereof. Preferred feedstocks are metallic gallium and gallium nitride and mixtures thereof. Most preferably, the feedstock is metallic gallium or gallium nitride. If other elements of Group XIII are to be incorporated into the gallium-containing nitride crystal, corresponding compounds or mixed compounds including Ga and the other Group XIII element can be used. If the substrate is to contain dopants or other additives, precursors thereof can be added to the feedstock.

[0067] The form of the feedstock is not particularly limited and it can be in the form of one or more pieces or in the form of a powder. If the feedstock is in the form of a powder, care should be taken that individual powder particles are not transported from the dissolution zone to the crystallization zone, where they can cause irregular crystallization. It is preferable that the feedstock is in one or more pieces and that the surface area of the feedstock is larger than that of the crystallization seed.

[0068] The nitrogen-containing solvent employed in the present invention must be able to form a supercritical fluid, in which gallium can be dissolved in the presence of alkali metal ions. Preferably the solvent is ammonia, a derivative thereof or mixtures thereof. An example of a suitable ammonia derivative is hydrazine. Most preferably the solvent is ammonia. To reduce corrosion of the reactor and to avoid side-reactions, halogens e.g. in the form of halides are preferably not intentionally added into the reactor. Although traces of halogens may be introduced into the system in the form of unavoidable impurities of the starting materials, care should be taken to keep the amount of halogen as low as possible. Due to the use of a nitrogen-containing solvent such as ammonia it is not necessary to include nitride compounds into the feedstock. Metallic gallium (or aluminum or indium) can be employed as the source material while the solvent provides the nitrogen required for the nitride formation.

[0069] It has been observed that the solubility of gallium-containing feedstock, such as gallium and corresponding elements of Group XIII and/or their compounds, can be significantly improved by the presence of at least one type of alkali metal-containing component as a solubilization aid (“mineralizer”). Lithium, sodium and potassium are preferred as alkali metals, wherein sodium and potassium are more preferred. The mineralizer can be added to the supercritical solvent in elemental form or preferably in the form of its compound. Generally the choice of the mineralizer depends on the solvent employed in the process. According to our investigations, alkali metal having a smaller ion radius can provide lower solubility of gallium-containing nitride in the supercritical ammonia solvent than that obtained with alkali metals having a larger ion radius. For example, if the mineralizer is in the form of a compound, it is preferably an alkali metal hydride such as MH, an alkali metal nitride such as M₃N, an alkali metal amide such as MNH₂, an alkali metal imide such as M₂NH or an alkali metal azide such as MN₃ (wherein M is an alkali metal). The concentration of the mineralizer is not particularly restricted and is selected so as to ensure adequate levels of solubility of both feedstock (the starting material) and gallium-containing nitride (the resulting product). It is usually in the range of 1:200 to 1:2, in the terms of the mols of the metal ion based on the mols of the solvent (molar ratio). In a preferred embodiment the concentration is from 1:100 to 1:5, more preferably 1:20 to 1:8 mols of the metal ion based on the mols of the solvent.

[0070] The presence of the alkali metal in the process can lead to alkali metal elements in the thus prepared substrates. It is possible that the amount of alkali metal elements is more than about 0.1 ppm, even more than 10 ppm. However, in these amounts the alkali metals do not detrimentally effect the properties of the substrates. It has been found that even at an alkali metal content of 500 ppm, the operational parameters of the substrate according to the invention are still satisfactory.

[0071] The dissolved feedstock crystallizes in the crystallization step under the low solubility conditions on the crystallization seed(s) which are provided in the container. The process of the invention allows bulk growth of monocrystalline gallium-containing nitride on the crystallization seed(s) and in particular leads to the formation of stoichiometric nitride in the form of a monocrystalline bulk layer on the crystallization seed(s).

[0072] Various crystals can be used as crystallization seeds in the present invention, however, it is preferred that the chemical and crystallographic constitution of the crystallization seeds is similar to those of the desired layer of bulk monocrystalline gallium-containing nitride. Therefore, the crystallization seed preferably comprises a crystalline layer of gallium-containing nitride and optionally one or more other elements of Group XIII. To facilitate crystallization of the dissolved feedstock, the defects surface density of the crystallization seed is preferably less than 10⁶/cm². Suitable crystallization seeds generally have a surface area of 8×8 mm² or more and thickness of 100 μm or more, and can be obtained e.g. by HVPE.

[0073] After the starting materials have been introduced into the container and the nitrogen-containing solvent has been brought into its supercritical state, the gallium-containing feedstock is at least partially dissolved at a first temperature and a first pressure, e.g. in the dissolution zone of an autoclave. Gallium-containing nitride crystallizes on the crystallization seed (e.g. in the crystallization zone of an autoclave) at a second temperature and at a second pressure while the nitrogen-containing solvent is in the supercritical state, wherein the second temperature is higher than the first temperature and/or the second pressure is lower than the first pressure. If the dissolution and the crystallization steps take place simultaneously in the same container, the second pressure is essentially equal to the first pressure.

[0074] This is possible since the solubility of gallium-containing nitride under the conditions of the present invention shows a negative temperature coefficient and a positive pressure coefficient in the presence of alkali metal ions. Without wishing to be bound by theory, it is postulated that the following processes occur. In the dissolution zone, the temperature and pressure are selected such that the gallium-containing feedstock is dissolved and the nitrogen-containing solution is undersaturated with respect to gallium-containing nitride. At the crystallization zone, the temperature and pressure are selected such that the solution, although it contains approximately the same concentration of gallium as in the dissolution zone, is over-saturated with respect to gallium-containing nitride. Therefore, crystallization of gallium-containing nitride on the crystallization seed occurs. This is illustrated in FIG. 15. Due to the temperature gradient, pressure gradient, concentration gradient, different chemical or physical character of dissolved feedstock and crystallized product etc., gallium is transported in a soluble form from the dissolution zone to the crystallization zone. In the present invention this is referred to as chemical transport of gallium-containing nitride in the supercritical solution. It is postulated that the soluble form of gallium is a gallium complex compound, with Ga atom in the coordination center surrounded by ligands, such as NH₃ molecules or its derivatives, like NH₂ ⁻, NH²⁻, etc.

[0075] This theory is equally applicable for all gallium-containing nitrides, such as AlGaN, InGaN and AlInGaN as well as GaN (the mentioned formulas are only intended to give the components of the nitrides. It is not intended to indicate their relative amounts). In such cases also aluminum and/or indium in a soluble form have to be present in the supercritical solution.

[0076] In a preferred embodiment of the invention, the gallium-containing feedstock is dissolved in at least two steps. In this embodiment, the gallium-containing feedstock generally comprises two kinds of starting materials which differ in solubility. The difference in solubility can be achieved chemically (e.g. by selecting two different chemical compounds) or physically (e.g. by selecting two forms of the same compound having definitely different surface areas, like microcrystalline powder and big crystals). In a preferred embodiment, the gallium-containing feedstock comprises two different chemical compounds such as metallic gallium and gallium nitride which dissolve at different rates. In a first dissolution step, the first component of the gallium-containing feedstock is substantially completely dissolved at a dissolution temperature and at a dissolution pressure in the dissolution zone. The dissolution temperature and the dissolution pressure, which can be set only in the dissolution zone or preferably in the whole container, are selected so that the second component of the gallium-containing feedstock and the crystallization seed(s) remain substantially undissolved. This first dissolution step results in an undersaturated or at most saturated solution with respect to gallium-containing nitride. For example, the dissolution temperature can be 100° C. to 350° C., preferably from 150° C. to 300° C. The dissolution pressure can be 0.1 kbar to 5 kbar, preferably from 0.1 kbar to 3 kbar. Generally the dissolution temperature is lower than the first temperature.

[0077] Subsequently the conditions in the crystallization zone are set at a second temperature and at a second pressure so that over-saturation with respect to gallium-containing nitride is obtained and crystallization of gallium-containing nitride occurs on the at least one crystallization seed. Simultaneously the conditions in the dissolution zone are set at a first temperature and at a first pressure (practically equal to the second pressure) so that the second component of the gallium-containing feedstock is now dissolved (second dissolution step). As explained above the second temperature is higher than the first temperature and/or the second pressure is lower than the first pressure so that the crystallization can take advantage of the negative temperature coefficient of solubility and/or by means of the positive pressure coefficient of solubility. Preferably the first temperature is also higher than the dissolution temperature. During the second dissolution step and the crystallization step, the system should be in a stationary state so that the concentration of gallium in the supercritical solution remains substantially constant, i.e. the same amount of gallium should be dissolved per unit of time as is crystallized in the same unit of time. This allows for the growth of gallium-containing nitride crystals of especially high quality and large size.

[0078] Typical pressures for the crystallization step and the second dissolution step are in the range of 1 to 10 kbar, preferably 1 to 5.5 and more preferably 1.5 to 3 kbar. The temperature is in the range of 100 to 800° C., preferably 300 to 600° C., more preferably 400 to 550° C. The difference in temperature should be at least 1° C., and preferably from 5° C. to 150° C. As explained above, the temperature difference between the dissolution zone and crystallization zone should be controlled so as to ensure a chemical transport in the supercritical solution, which takes place through convection in an autoclave.

[0079] In the process of the invention, the crystallization should take place selectively on the crystallization seed and not on a wall of the container. Therefore, the over-saturation extent with respect to the gallium-containing nitride in the supercritical solution in the crystallization zone should be controlled so as to be below the spontaneous crystallization level where crystallization takes place on a wall of the autoclave as well as on the seed, i.e. the level at which spontaneous crystallization occurs. This can be achieved by adjusting the chemical transport rate and the crystallization temperature and/or pressure. The chemical transport is related on the speed of a convection flow from the dissolution zone to the crystallization zone, which can be controlled by the temperature difference between the dissolution zone and the crystallization zone, the size of the opening(s) of baffle(s) between the dissolution zone and the crystallization zone and so on.

[0080] The performed tests showed that the best bulk monocrystalline gallium nitride obtained had the dislocation density close to 10⁴/cm² with simultaneous FWHM of X-ray rocking curve from (0002) plane below 60 arcsec, providing an appropriate quality and durability for optic semiconductor devices produced with its use. The gallium-containing nitride of the present invention typically has a wurzite structure.

[0081] Feedstock material can also be prepared using a method similar to those described above. The method involves the steps of:

[0082] (i) providing a gallium-containing feedstock, an alkali metal-containing component, at least one crystallization seed and a nitrogen-containing solvent in a container having at least one zone;

[0083] (ii) subsequently bringing the nitrogen-containing solvent into a supercritical state;

[0084] (iii) subsequently dissolving the gallium-containing feedstock (such as metallic gallium or aluminium or indium, preferably metallic gallium) at a dissolution temperature and at a dissolution pressure, whereby the gallium-containing feedstock is substantially completely dissolved and the crystallization seed remains substantially undissolved so that an undersaturated solution with respect to gallium-containing nitride is obtained;

[0085] (iv) subsequently setting the conditions in the container at a second temperature and at a second pressure so that over-saturation with respect to gallium-containing nitride is obtained and crystallization of gallium-containing nitride occurs on the at least one crystallization seed;

[0086] wherein the second temperature is higher than the dissolution temperature.

[0087] The conditions described above with respect to the dissolution temperature and the second temperature also apply in this embodiment.

[0088] Gallium-containing nitride exhibits good solubility in supercritical nitrogen-containing solvents (e.g. ammonia), provided alkali metals or their compounds, such as KNH₂, are introduced into it. FIG. 1 shows the solubility of gallium-containing nitride in a supercritical solvent versus pressure for temperatures of 400 and 500° C. wherein the solubility is defined by the molar percentage: S_(m)≡GaN^(solvent):(KNH₂+NH₃) 100%. In the presented case the solvent is the KNH₂ solution in supercritical ammonia of a molar ratio x≡KNH₂:NH₃ equal to 0.07. For this case S_(m) should be a smooth function of only three parameters: temperature, pressure, and molar ratio of mineralizer (i.e. S_(m)=S_(m)(T, p, x)). Small changes of S_(m) can be expressed as:

ΔS _(m)≈(δS _(m) /δT)|_(p,x) ΔT+(δS _(m) .δp)|_(T,x) Δp+(δS _(m) /δx)|_(T,p) Δx,

[0089] where the partial differentials (e.g. (δS_(m)/δ_(T))|_(p,x)) determine the behavior of S_(m) with variation of its parameters (e.g. T). In this specification the partial differentials are called “coefficients” (e.g. (δS_(m)/δT)|_(p,x) is a “temperature coefficient of solubility”).

[0090] The diagram shown FIG. 1 illustrates that the solubility increases with pressure and decreases with temperature, which means that it possesses a negative temperature coefficient and a positive pressure coefficient. Such features allow obtaining a bulk monocrystalline gallium-containing nitride by dissolution in the higher solubility conditions, and crystallization in the lower solubility conditions. In particular, the negative temperature coefficient means that, in the presence of temperature gradient, the chemical transport of gallium in a soluble form can take place from the dissolution zone having a lower temperature to the crystallization zone having a higher temperature.

[0091] The process according to invention allows the growth of bulk monocrystalline gallium-containing nitride on the seed and leads in particular to creation of stoichiometric gallium nitride, obtained in the form of monocrystalline bulk layer grown on a gallium-nitride seed. Since such a monocrystal is obtained in a supercritical solution that contains ions of alkali metals, it contains also alkali metals in a quantity higher than 0.1 ppm. Because it is desired to maintain a purely basic character of a supercritical solution, mainly in order to avoid corrosion of the apparatus, halides are preferably not intentionally introduced into the solvent. The process of the invention can also provide a bulk monocrystalline gallium nitride in which part of the gallium, e.g. from 0.05 to 0.5 may be substituted by Al and/or In. Moreover, the bulk monocrystalline gallium nitride may be doped with donor and/or acceptor and/or magnetic dopants. These dopants can modify optical, electric and magnetic properties of a gallium-containing nitride. With respect to the other physical properties, the bulk monocrystalline gallium nitride can have a dislocation density below 10⁶/cm², preferably below 10⁵/cm², or most preferably below 10⁴/cm². Besides, the FWHM of the X-ray rocking curve from (0002) plane can be below 600 arcsec, preferably below 300 arcsec, and most preferably below 60 arcsec. The best bulk monocrystalline gallium nitride obtained may have dislocation density lower than 10⁴/cm² and simultaneously a FWHM of X-ray rocking curve from (0002) plane below 60 arcsec.

[0092] Due to the good crystalline quality the obtained gallium-containing nitride crystals obtained in the present invention, they may be used as a substrate material for optoelectronic semiconductor devices based on nitrides, in particular for laser diodes.

[0093] The following examples are intended to illustrate the invention and should not be construed as being limiting.

EXAMPLES

[0094] Since it is not possible to readily measure the temperature in an autoclave while in use under supercritical conditions, the temperature in the autoclave was estimated by the following method. The outside of the autoclave is equipped with thermocouples near the dissolution zone and the crystallization zone. For the calibration, additional thermocouples were introduced into the inside of the empty autoclave in the dissolution zone and the crystallization zone. The empty autoclave was then heated stepwise to various temperatures and the values of the temperature of the thermocouples inside the autoclave and outside the autoclave were measured and tabulated. For example, if the temperature of the crystallization zone is determined to be 500° C. and the temperature of the dissolution zone is 400° C. inside the empty autoclave when the temperature measured by the outside thermocouples are 480° C. and 395° C., respectively. It is assumed that under supercritical crystallization conditions the temperatures in the crystallization/dissolution zones will also be 500/400° C. when temperatures of 480/395° C. are measured by the outside thermocouples. In reality, the temperature difference between the two zones can be lower due to effective heat transfer through the supercritical solution.

Example 1

[0095] Two crucibles were placed into a high-pressure autoclave having a volume of 10.9 cm³. The autoclave is manufactured according to a known design [H. Jacobs, D. Schmidt, Current Topics in Materials Science, vol. 8, ed. E. Kaldis (North-Holland, Amsterdam, 1981), 381]. One of the crucibles contained 0.4 g of gallium nitride in the form of 0.1 mm thick plates produced by the HVPE method as feedstock, while other contained a gallium nitride seed of a double thickness weighing 0.1 g. The seed was also obtained by the HVPE method. Further, 0.72 g of metallic potassium of 4N purity was placed in the autoclave, the autoclave was filled with 4.81 g of ammonia and then closed. The autoclave was put into a furnace and heated to the temperature of 400° C. The pressure within the autoclave was 2 kbar. After 8 days the temperature was increased to 500° C., while the pressure was maintained at the 2 kbar level and the autoclave was maintained under these conditions for another 8 days (FIG. 2). As a result of this process, in which the dissolution and crystallization steps were separated in time, the feedstock was completely dissolved and the recrystallization of gallium nitride layer took place on the partially dissolved seed. The two-sided monocrystalline layers had a total thickness of about 0.4 mm.

Example 2

[0096] Two crucibles were put into the above-mentioned high-pressure autoclave having a volume of 10.9 cm³. One of the crucibles contained 0.44 g of gallium nitride in the form of 0.1 mm thick plates produced by the HVPE method as feedstock, and the other contained a gallium nitride seed of a double thickness weighing 0.1 g, also obtained by the HVPE method. Further, 0.82 g of metallic potassium of 4N purity was placed in the autoclave, the autoclave was filled with 5.43 g of ammonia and then closed. The autoclave was put into a furnace and heated to temperature of 500° C. The pressure within the autoclave was 3.5 kbar. After 2 days the pressure was lowered to 2 kbar, while the temperature was maintained at the 500° C. level and the autoclave was maintained under these conditions for another 4 days (FIG. 3). As a result of this process, the feedstock was completely dissolved and the recrystallization of gallium nitride took place on the partially dissolved seed. The two-sided monocrystalline layers had a total thickness of about 0.25 mm.

Example 3

[0097] Two crucibles were placed into the above-mentioned high-pressure autoclave having a volume of 10.9 cm³. One of the crucibles contained 0.3 g of the feedstock in the form of metallic gallium of 6N purity and the other contained a 0.1 g gallium nitride seed obtained by the HVPE method. Further, 0.6 g of metallic potassium of 4N purity was placed in the autoclave; the autoclave was filled with 4 g of ammonia and then closed. The autoclave was put into a furnace and heated to temperature of 200° C. After 2 days the temperature was increased to 500° C., while the pressure was maintained at the 2 kbar level and the autoclave was maintained in these conditions for further 4 days (FIG. 4). As a result of this process, the feedstock was completely dissolved and the crystallization of gallium nitride took place on the seed. The two-sided monocrystalline layers had a total thickness of about 0.3 mm.

Example 4

[0098] This is an example of process, in which the dissolution and crystallization steps take place simultaneously (recrystallization process). In this example and all the following an apparatus is used which is schematically shown in FIG. 9. The basic unit of the apparatus is the autoclave 1, which in this Example has a volume of 35.6 cm³. The autoclave 1 is equipped with an installation 2 for providing chemical transport of the solvent in a supercritical solution inside the autoclave 1. For this purpose, the autoclave 1 is put into a chamber 3 of a set of two furnaces 4 provided with heating devices 5 and a cooling devices 6. The autoclave 1 is secured in a desired position with respect to the furnaces 4 by means of a screw-type blocking device 7. The furnaces 4 are mounted on a bed 8 and are secured by means of steel tapes 9 wrapped around the furnaces 4 and the bed 8. The bed 8 together with the set of furnaces 4 is rotationally mounted in base 10 and is secured in a desired angular position by means of a pin interlock 11. In the autoclave 1, placed in the set of furnaces 4, the convective flow of supercritical solution takes place as determined by the installation 2. The installation 2 is in the form of a horizontal baffle 12 having a central opening. The baffle 12 separates the dissolution zone 13 from the crystallization zone 14 in the autoclave 1, and enables, together with the adjustable tilting angle of the autoclave 1, controlling of speed and type of convective flow. The temperature level of the individual zones in the autoclave 1 is controlled by means of a control system 15 operating the furnaces 4. In the autoclave 1, the dissolution zone 13 coincides with the low-temperature zone of the set of furnaces 4, is located above the horizontal baffle 12 and the feedstock 16 is put into this zone 13. On the other hand, the crystallization zone 14 coincides with the high-temperature zone of the set of furnaces 4 and it is located below the horizontal baffle 12. The seed 17 is mounted in this zone 14. The mounting location of the seed 17 is below the intersection of the rising and descending convective streams.

[0099] An amount of 3.0 g of gallium nitride produced by the HVPE method was placed in the high-pressure autoclave described above, which was set in the horizontal position. This gallium nitride had the form of plates of about 0.2 mm thickness, and it was distributed (roughly uniformly) in equal portions in the dissolution zone 13 and the crystallization zone 14. The portion placed in the dissolution zone 13 played the role of feedstock, whereas the portion placed in the crystallization zone 14 played the role of crystallization seeds. Metallic potassium of 4N purity was also added in a quantity of 2.4 g. Then the autoclave 1 was filled with 15.9 g of ammonia (5N), closed, put into a set of furnaces 4 and heated to a temperature of 450° C. The pressure inside the autoclave 1 was approx. 2 kbar. During this stage, which lasted one day, a partial dissolution of gallium nitride was carried out in both zones. Then the temperature of the crystallization zone 14 was increased to 500° C. while the temperature of the dissolution zone 13 was lowered to 400° C. and the autoclave 1 was kept in these conditions for 6 more days (FIG. 5). As a final result of this process, partial dissolution of the feedstock in the dissolution zone 13 and crystallization of gallium nitride on the gallium nitride seeds in the crystallization zone 14 took place.

Example 5

[0100] The above-mentioned high pressure autoclave 1 having a volume of 35.6 cm³ was charged with feedstock in the form of a 3.0 g pellet of sintered gallium nitride (introduced into the dissolution zone 13) two seeds of gallium nitride obtained by the HVPE method and having the form of plates having a thickness of 0.4 mm and total weight of 0.1 g (introduced into the crystallization zone 14), as well as with 2.4 g of metallic potassium of 4N purity. Then the autoclave was filled with 15.9 g of ammonia (5N) and closed. The autoclave 1 was then put into a set of furnaces 4 and heated to 450° C. The pressure inside the autoclave was about 2 kbar. After an entire day the temperature of the crystallization zone 14 was raised to 480° C., while the temperature of dissolution zone 13 was lowered to 420° C. and the autoclave was maintained under these conditions for 6 more days (see FIG. 6). As a result of the process the feedstock was partially dissolved in the dissolution zone 13 and gallium nitride crystallized on the seeds in the crystallization zone 14. The two-sided monocrystalline layers had total thickness of about 0.2 mm.

Example 6

[0101] The above-mentioned high pressure autoclave 1 having a volume of 35.6 cm³ (see FIG. 9) was charged with 1.6 g of feedstock in the form of gallium nitride produced by the HVPE method and having the form of plates having a thickness of about 0.2 mm (introduced into the dissolution zone 13), three gallium-nitride seeds of a thickness of about 0.35 mm and a total weight of 0.8 g, also obtained by the HVPE method (introduced into the crystallization zone 14), as well as with 3.56 g of metallic potassium of 4N purity. The autoclave 1 was filled with 14.5 g of ammonia (5N) and closed. Then the autoclave 1 was put into a set of furnaces 4 and heated to 425° C. The pressure inside the autoclave was approx. 1.5 kbar. After an entire day the temperature of dissolution zone 13 was lowered to 400° C. while the temperature of crystallization zone 14 was increased to 450° C. and the autoclave was kept in these conditions for 8 more days (see FIG. 7). After the process, the feedstock was found to be partially dissolved in the dissolution zone 13 and gallium nitride had crystallized on the seeds of the HVPE GaN in the crystallization zone 14. The two-sided monocrystalline layers had a total thickness of about 0.15 mm.

Example 7

[0102] The above-mentioned high pressure autoclave 1 having a volume of 35.6 cm³ (see FIG. 9) was charged in its dissolution zone 13 with 2 g of feedstock in the form of gallium nitride produced by the HVPE method and having the form of plates having a thickness of about 0.2 mm, and 0.47 g of metallic potassium of 4N purity, and in its crystallization zone 14 with three GaN seeds of a thickness of about 0.3 mm and a total weight of about 0.3 g also obtained by the HVPE method. The autoclave was filled with 16.5 g of ammonia (5N) and closed. Then the autoclave 1 was put into a set of furnaces 4 and heated to 500° C. The pressure inside the autoclave was approx. 3 kbar. After an entire day the temperature in the dissolution zone 13 was reduced to 450° C. while the temperature in the crystallization zone 14 was raised to 550° C. and the autoclave was kept under these conditions for the next 8 days (see FIG. 8). After the process, the feedstock was found to be partially dissolved in the dissolution zone 13 and gallium nitride had crystallized on seeds in the crystallization zone 14. The two-sided monocrystalline layers had a total thickness of about 0.4 mm.

Example 8

[0103] An amount of 1.0 g of gallium nitride produced by the HVPE method was put into the dissolution zone 13 of the high-pressure autoclave 1 having a volume of 35.6 cm³. In the crystallization zone 14 of the autoclave, a seed crystal of gallium nitride having a thickness of 100 μm and a surface area of 2.5 cm², obtained by the HVPE method, was placed. Then the autoclave was charged with 1.2 g of metallic gallium of 6N purity and 2.2 g of metallic potassium of 4N purity. Subsequently, the autoclave 1 was filled with 15.9 g of ammonia (5N), closed, put into a set of furnaces 4 and heated to a temperature of 200° C. After 3 days during which period metallic gallium was dissolved in the supercritical solution. The temperature was increased to 450° C. which resulted in a pressure of about 2.3 kbar. The next day, the crystallization zone temperature was increased to 500° C. while the temperature of the dissolution zone 13 was lowered to 370° C. and the autoclave 1 was kept in these conditions for the next 20 days (see FIG. 11). As a result of this process, the partial dissolution of the material in the dissolution zone 13 and the growth of the gallium nitride on gallium nitride seeds in the crystallization zone 14 took place. The resulting crystal of gallium nitride having a total thickness of 350 μm was obtained in the form of two-sided monocrystalline layers.

Example 9

[0104] An amount of 3.0 g of gallium nitride in the form of a sintered gallium nitride pellet was put into the dissolution zone 13 of high-pressure autoclave 1 having a volume of 35.6 cm³ (see FIG. 9). In the crystallization zone 14 of the autoclave, a seed crystal of gallium nitride obtained by the HVPE method and having a thickness of 120 μm and a surface area of 2.2 cm² was placed. Then the autoclave was charged with 2.3 g of metallic potassium of 4N purity. Subsequently, the autoclave 1 was filled with 15.9 g of ammonia (5N), closed, put into a set of furnaces 4 and heated to a temperature of 250° C. in order to partially dissolve the sintered GaN pellet and obtain a preliminary saturation of a supercritical solution with gallium in the soluble form. After two days, the crystallization zone 14 temperature was increased to 500° C. while the temperature of the dissolution zone 13 was lowered to 420° C. and the autoclave 1 was kept in these conditions for the next 20 days (see FIG. 12). As a result of this process, partial dissolution of the material in the dissolution zone 13 and the growth of gallium nitride on the gallium nitride seed took place in the crystallization zone 14. A crystal of gallium nitride having a total thickness of 500 μm was obtained in the form of two-sided monocrystalline layers.

Example 10

[0105] An amount of 0.5 g of gallium nitride plates having an average thickness of about 120 μm, produced by the HVPE method, were put into the dissolution zone 13 of high-pressure autoclave 1 having a volume of 35.6 cm³. In the crystallization zone 14 of the autoclave, three seed crystals of gallium nitride obtained by the HVPE method were placed. The seed crystals had a thickness of about 120 μm and a total surface area of 1.5 cm². Then the autoclave was charged with 0.41 g of metallic lithium of 3N purity. Subsequently, the autoclave 1 was filled with 14.4 g of ammonia (5N), closed, put into a set of furnaces 4 and heated so that the temperature of the crystallization zone 14 was increased to 550° C. and the temperature of the dissolution zone 13 was increased to 450° C. The resulting pressure was about 2.6 kbar. The autoclave 1 was kept in these conditions for the next 8 days (see FIG. 13). As a result of this process, partial dissolution of the material in the dissolution zone 13 and growth of gallium nitride on the gallium nitride seeds in the crystallization zone 14 took place. The resulting crystals of gallium nitride had a thickness of 40 μm and were in the form of two-sided monocrystalline layers.

Example 11

[0106] An amount of 0.5 g of gallium nitride having an average thickness of about 120 μm, produced by the HVPE method, was placed into the dissolution zone 13 of high-pressure autoclave 1 having a volume of 35.6 cm³. In the crystallization zone 14 of the autoclave, three seed crystals of gallium nitride obtained by the HVPE method were placed. The seed crystals had a thickness of 120 μm and a total surface area of 1.5 cm². Then the autoclave was charged with 0.071 g of metallic gallium of 6N purity and 1.4 g of metallic sodium of 3N purity. Subsequently, the autoclave 1 was filled with 14.5 g of ammonia (5N), closed, put into a set of furnaces 4 and heated to temperature of 200° C. After 1 day—during which period metallic gallium was dissolved in the supercritical solution—the autoclave 1 was heated so that the temperature in the crystallization zone was increased to 500° C., while the temperature in the dissolution zone was increased to 400° C. The resulting pressure was about 2.3 kbar. The autoclave 1 was kept in these conditions for the next 8 days (see FIG. 14). As a result of this process, partial dissolution of the material in the dissolution zone 13 and growth of gallium nitride on gallium nitride seeds in the crystallization zone 14 took place. The resulting crystals of gallium nitride were obtained in the form of two-sided monocrystalline layers having a total thickness of 400 μm.

Example 12

[0107] An amount of 0.5 g of gallium nitride having an average thickness of about 120 μm, produced by the HVPE method, was placed into the dissolution zone 13 of the high-pressure autoclave 1 having a volume of 35.6 cm³. In the crystallization zone 14 of the autoclave, three seed crystals of gallium nitride obtained by the HVPE method were placed. The seed crystals had a thickness of 120 μm and a total surface area of 1.5 cm². Then the autoclave was charged with 0.20 g of gallium amide and 1.4 g of metallic sodium of 3N purity. Subsequently, the autoclave 1 was filled with 14.6 g of ammonia (5N), closed, put into a set of furnaces 4 and heated to a temperature of 200° C. After 1 day during which period gallium amide was dissolved in the supercritical solution—the autoclave 1 was heated so that the temperature in the crystallization zone was increased to 500° C., while the temperature in the dissolution zone was increased to 400° C. The resulting pressure was about 2.3 kbar. The autoclave 1 was kept in these conditions for the next 8 days (see also FIG. 14). As a result of this process, partial dissolution of the material in the dissolution zone 13 and growth of gallium nitride on gallium nitride seeds in the crystallization zone 14 took place. The resulting crystals of gallium nitride were in the form of two-sided monocrystalline layers having a total thickness of 490 μm.

Example 13

[0108] One crucible was placed into the above-mentioned high-pressure autoclave having a volume of 10.9 cm³. The crucible contained 0.3 g of the feedstock in the form of metallic gallium of 6N purity. Also three gallium-nitride seeds having a thickness of about 0.5 mm and a total mass of 0.2 g, all obtained by the HVPE method, were suspended within the reaction chamber. Further, 0.5 g of metallic sodium of 3N purity was placed in the autoclave; the autoclave was filled with 5.9 g of ammonia and then closed. The autoclave was put into a furnace and heated to a temperature of 200° C., where the pressure was about 2.5 kbar. After 1 day the temperature was increased to 500° C., while the pressure increased up to 5 kbar and the autoclave was maintained in these conditions for further 2 days. As a result of this process, the feedstock was completely dissolved and the crystallization of gallium nitride took place on the seed. The average thickness of the two-side-overgrown monocrystalline layer of gallium nitride was about 0.14 mm. The FWHM of the X-ray rocking curve from the (0002) plane at the gallium-terminated side was 43 arcsec, while at the nitrogen-terminated side it was 927 arcsec.

[0109] The monocrystalline layers have a wurzite structure like in all of the other examples. 

What is claimed is:
 1. A process for obtaining a bulk monocrystalline gallium-containing nitride in an autoclave having a gallium-containing feedstock in one zone, a seed in another zone and a supercritical solvent containing ions of alkali metals therein, said process comprising the steps of: dissolving the gallium-containing feedstock in the supercritical solvent to form a supercritical solution at a first temperature; and crystallizing the gallium-containing nitride from the supercritical solution on the seed at a second temperature higher than the first temperature at which the feedstock dissolves in the supercritical solvent.
 2. The process according to claim 1, wherein said step of dissolving the gallium-containing feedstock includes dissolving the gallium-containing feedstock in a dissolution zone and transferring the supercritical solution to the another zone at the second temperature.
 3. The process according to claim 1, further comprising the steps of substantially simultaneously creating at least two zones of different temperatures in the autoclave.
 4. The process according to claim 3, wherein the another zone is a crystallization zone and further comprising the step of controlling the temperature difference between the dissolution zone and the crystallization zone so as to ensure chemical transport in the supercritical solution.
 5. The process according to claim 4, wherein said step of controlling the temperature difference includes allowing convection in the autoclave for chemical transport in the supercritical solution.
 6. The process according to claim 4, wherein said step of controlling the temperature difference between the dissolution zone and the crystallization zone inside the autoclave includes controlling the temperature difference so that it is greater than 1° C.
 7. The process according to claim 1, wherein said step of crystallizing gallium-containing nitride includes crystallizing a gallium-containing nitride having the form of Al_(x)Ga_(1-x-y)In_(y)N, where 0≦x<1, 0≦y<1, 0≦x+y<1.
 8. The process according to claim 1, further comprising the step of adding at least one dopant of a donor, acceptor and magnetic type.
 9. The process according to claim 1, further comprising the step of providing the supercritical solvent including at least one of NH₃ and its derivatives in the autoclave.
 10. The process according to claim 1, further comprising the step of providing the supercritical solvent including at least potassium ions in the autoclave.
 11. The process according to claim 1, further comprising the step of providing the gallium-containing feedstock including at least one of a gallium-containing nitride and its precursors in the autoclave.
 12. The process according to claim 11, wherein said step of providing the gallium-containing feedstock includes providing precursors selected from a group consisting of azides, imides, amido-imides, amides, hydrides, metallic compounds and gallium-containing alloys, and metallic gallium.
 13. The process according to claim 1, further comprising providing the seed having at least a crystalline layer of at least one of a gallium-containing nitride and other elements of Group XIII.
 14. The process according to claim 1, further comprising the step of providing the seed having at least a crystalline layer of gallium-containing nitride with a dislocation density below 10⁶/cm².
 15. The process according to claim 1, wherein said step of crystallizing at a second temperature includes crystallizing at temperatures from 100 to 800° C.
 16. The process according to claim 15, wherein said step of crystallizing at a second temperature includes crystallizing at temperatures from 400 to 600° C.
 17. The process according to claim 16, wherein said step of crystallizing at a second temperature includes crystallizing at temperatures from 450 to 550° C.
 18. The process according to claim 1, wherein said step of crystallizing includes crystallizing at pressures from 100 to 10000 bar.
 19. The process according to claim 18, wherein said step of crystallizing includes crystallizing at pressures from 1000 to 5000 bar.
 20. The process according to claim 19, wherein said step of crystallizing includes crystallizing at pressures from 1500 to 3000 bar.
 21. The process according to claim 1, further comprising the step of controlling the content of alkali metal ions in the supercritical solvent so as to provide adequate levels of solubility of the feedstock and the gallium-containing nitride.
 22. The process according to claim 1, further comprising the step of controlling the molar ratio of the alkali-metal ions to the remaining components in the supercritical solvent within a range of 1:200 to 1:2.
 23. The process according to claim 22, further comprising the step of controlling the molar ratio of the alkali-metal ions to the remaining components in the supercritical solvent within a range of 1:50 to 1:5.
 24. The process according to claim 23, further comprising the step of controlling the molar ratio of the alkali-metal ions to the remaining components in the supercritical solvent within a range of 1:20 to 1:5.
 25. A process for preparing a bulk monocrystalline gallium-containing nitride crystal in an autoclave, which comprises the steps of (i) providing a supercritical ammonia solution containing ions of alkali metal and gallium in a soluble form by introducing a gallium-containing feedstock to supercritical ammonia solvent containing ions of alkali metals, in which solubility of gallium-containing nitride shows a negative temperature coefficient in said supercritical ammonia solution, and (ii) crystallizing said gallium-containing nitride selectively on a crystallization seed from said supercritical ammonia solution by means of the negative temperature coefficient of solubility.
 26. A process for preparing a bulk monocrystalline gallium-containing nitride in an autoclave according to claim 25, wherein said gallium-containing nitride is GaN.
 27. A process for preparing a bulk monocrystalline gallium-containing nitride in an autoclave according to claim 25, wherein said ion of alkali metal is selected from the group consisting of Li⁺, Na⁺, and K⁺.
 28. A process for preparing a bulk monocrystalline gallium-containing nitride in an autoclave according to claim 25, wherein said ions of alkali metals are introduced in the form of mineralizers selected from alkali metals and compounds thereof, such as azides, nitrides, amides, amido-imides, imides, and/or hydrides, for forming an ammono-basic supercritical ammonia solution, which does not contain ions of halogens.
 29. A process for preparing a bulk monocrystalline gallium-containing nitride in an autoclave according to claim 25, wherein said gallium-containing nitride is dissolved in said supercritical ammonia solvent in the form of gallium complex compounds containing alkali metals and NH₃ and/or its derivatives.
 30. A process for preparing a bulk monocrystalline gallium-containing nitride in an autoclave according to claim 25, wherein said gallium complex compound in said supercritical ammonia solution is formed from a dissolution of GaN and/or dissolution of metallic Ga with supercritical ammonia solvent.
 31. A process for preparing a bulk monocrystalline gallium-containing nitride in an autoclave, which comprises the steps of (i) providing a supercritical ammonia solution containing ions of alkali metal and gallium in a soluble form by introducing a gallium-containing feedstock into a supercritical ammonia solvent containing ions of alkali metals, in which solubility of gallium-containing nitride shows a positive pressure coefficient in said supercritical ammonia solution, and (ii) crystallizing said gallium-containing nitride selectively on a crystallization seed from said supercritical ammonia solution by means of the positive pressure coefficient of solubility.
 32. A process for preparing a bulk monocrystalline gallium-containing nitride in an autoclave according to claim 31, wherein said gallium-containing nitride is GaN.
 33. A process for preparing a bulk monocrystalline gallium-containing nitride in an autoclave according to claim 31, wherein said ion of alkali metal is selected from the group consisting of Li⁺, Na⁺, and K⁺.
 34. A process for preparing a bulk monocrystalline gallium-containing nitride in an autoclave according to claim 31, wherein said ions of alkali metals are introduced in the form of mineralizers selected from alkali metals and compounds thereof, such as azides, nitrides, amides, amido-imides, imides, and/or hydrides, for forming an ammono-basic supercritical ammonia solution, which does not contain ions of halogens.
 35. A process for preparing a bulk monocrystalline gallium-containing nitride in an autoclave according to claim 31, wherein said gallium-containing nitride is dissolved in said supercritical ammonia solvent in the form of gallium complex compounds containing alkali metals and NH₃ and/or its derivatives.
 36. A process for preparing a bulk monocrystalline gallium-containing nitride in an autoclave according to claim 31, wherein said gallium complex compound in said supercritical ammonia solution is formed from a dissolution of GaN and/or dissolution of metallic Ga with supercritical ammonia solvent.
 37. A process for preparing a supercritical ammonia solution containing gallium-containing nitride, which comprises the steps of (i) providing a supercritical ammonia solvent by means of adjusting a temperature and/or pressure in an autoclave and (ii) dissolving a precursor of gallium-containing nitride in said supercritical ammonia solvent to form soluble gallium complex compounds at a temperature lower than that at which dissolving of gallium-containing nitride takes place effectively.
 38. A process for preparing a supercritical ammonia solution containing gallium-containing nitride according to claim 37, wherein the step of dissolving said precursor in said supercritical ammonia solvent is carried out at a temperature of 150 to 300° C.
 39. A process for controlling the recrystallization of a gallium-containing nitride in a supercritical ammonia solution, which comprises the steps of (i) preparing a supercritical ammonia solution containing soluble gallium complex compounds formed by dissolving of gallium-containing nitride feedstock in an autoclave and (ii) decreasing the solubility of said gallium-containing nitride in the supercritical ammonia solution by increasing the temperature above that at which dissolving of the gallium-containing nitride feedstock is carried out.
 40. A process for controlling the recrystallization of a gallium-containing nitride in a supercritical ammonia solution which comprises the steps of (i) preparing a supercritical ammonia solution containing soluble gallium complex compounds formed by dissolving of gallium-containing nitride feedstock in the dissolution zone and (ii) controlling over-saturation of said supercritical ammonia solution with respect to the crystallization seed, while maintaining a temperature in the crystallization zone lower than that in the dissolution zone.
 41. A process for controlling recrystallization of a gallium-containing nitride in a supercritical ammonia solution according to claim 40, in which over-saturation of said supercritical solution with respect to said crystallization seed is maintained below the level where the phenomenon of spontaneous nucleation of gallium-containing nitride appears.
 42. A process for controlling recrystallization of a gallium-containing nitride in a supercritical ammonia solution according to claim 40, in which over-saturation of said supercritical ammonia solution with respect to said crystallization seed, is controlled by adjusting pressure and composition of the supercritical ammonia solvent.
 43. A process for controlling recrystallization of a gallium-containing nitride in a supercritical ammonia solution according to claim 40, in which over-saturation of said supercritical ammonia solution is controlled by adjusting the crystallization temperature.
 44. A process for controlling recrystallization of a gallium-containing nitride in a supercritical ammonia solution according to claim 40, in which over-saturation of said supercritical ammonia solution is controlled by adjusting the temperature difference between the dissolution zone and the crystallization zone.
 45. A process for controlling recrystallization of a gallium-containing nitride in a supercritical ammonia solution according to claim 40, in which over-saturation of said supercritical ammonia solution is controlled by adjusting the rate of chemical transport.
 46. A process for controlling recrystallization of a gallium-containing nitride in a supercritical ammonia solution according to claim 39, in which controlling solubility of said gallium-containing nitride in the supercritical ammonia solution is carried out by adjusting the convective flow between the dissolution zone and the crystallization zone.
 47. A process for controlling recrystallization of a gallium-containing nitride in a supercritical ammonia solution according to claim 39, in which controlling solubility of said gallium-containing nitride in the supercritical ammonia solution is carried out by adjusting the opening ratio of a baffle or baffles between the dissolution zone and the crystallization zone.
 48. A process for obtaining a gallium-containing nitride crystal, comprising the steps of: providing a gallium-containing feedstock, an alkali metal-containing component, at least one crystallization seed and a nitrogen-containing solvent in at least one container; bringing the nitrogen-containing solvent into a supercritical state; at least partially dissolving the gallium-containing feedstock at a first temperature and at a first pressure; and crystallizing gallium-containing nitride on the crystallization seed at a second temperature and at a second pressure while the nitrogen-containing solvent is in the supercritical state; wherein at least one of the following criteria is fulfilled: (a) the second temperature is higher than the first temperature; and (b) the second pressure is lower than the first pressure.
 49. The process according to claim 48, wherein the at least one container is an autoclave.
 50. The process according to claim 48, wherein the gallium-containing feedstock is at least partially dissolved before step (iv).
 51. The process according to claim 48, wherein the gallium-containing feedstock is at least partially dissolved during step (iv).
 52. The process according to claim 48, wherein the process is conducted in a container having a dissolution zone at the first temperature and a crystallization zone at the second temperature and wherein the second temperature is higher than the first temperature.
 53. The process according to claim 52, wherein the difference in temperature between the dissolution zone and crystallization zone is selected so as to ensure convective transport in the supercritical solution.
 54. The process according to claim 53, wherein the difference in temperature between the second temperature and the first temperature is at least 1° C.
 55. The process according to claim 54, wherein the difference in temperature between the second temperature and the first temperature is from about 5 to about 150° C.
 56. The process according to claim 48, wherein the gallium-containing nitride has the general formula Al_(x)Ga_(1-x-y)In_(y)N, where 0≦x<1, 0≦y<1, 0≦x+y<1.
 57. The process according to claim 56, wherein the gallium-containing nitride has the general formula Al_(x)Ga_(1-x-y)In_(y)N, where 0 x<0.5 and 0 y<0.5.
 58. The process according to claim 56, wherein the gallium-containing nitride is gallium nitride.
 59. The process according to claim 48, wherein the gallium-containing nitride further contains at least one donor dopant, at least one acceptor dopant, at least one magnetic dopant or mixtures thereof.
 60. The process according to claim 48, wherein the gallium-containing feedstock comprises at least one compound selected from the group consisting of gallium nitride, gallium azides, gallium imides, gallium amido-imides, gallium hydrides, gallium-containing alloys, metallic gallium and mixtures thereof.
 61. The process according to claim 60, wherein the gallium-containing feedstock comprises metallic gallium and gallium nitride.
 62. The process according to claim 60, wherein the feedstock further comprises an aluminium feedstock, an indium feedstock or mixtures thereof, wherein the feedstocks are selected from the group consisting of nitrides, azides, imides, amido-imides, hydrides, alloys, metallic aluminium, and metallic indium.
 63. The process according to claim 48, wherein the alkali metal-containing component is at least one metallic alkali metal or at least one alkali metal salt.
 64. The process according to claim 63, wherein the alkali metal in the alkali metal-containing component is lithium, sodium, potassium or cesium.
 65. The process according to claim 64, wherein the alkali metal in the alkali metal-containing component is sodium or potassium.
 66. The process according to claim 63, wherein the alkali metal salt is an amide, an imide or an azide.
 67. The process according to claim 48, wherein a surface of the at least one crystallization seed is a crystalline layer of a gallium-containing nitride.
 68. The process according to claim 67, wherein the gallium-containing nitride of the crystalline layer has the general formula Al_(x)Ga_(1-x-y)In_(y)N, where 0≦x<1, 0≦y<1, 0≦x+y<1.
 69. The process according to claim 67, wherein the crystalline layer has a dislocation density of less than 10⁶/cm².
 70. The process according to claim 48, wherein the nitrogen-containing solvent is ammonia, a derivative thereof, or mixtures thereof.
 71. The process according to claim 48, wherein the first temperature and the second temperature are from about 100° C. to about 800° C. and wherein the second temperature is at least 1° C. higher than the first temperature.
 72. The process according to claim 71, wherein the first temperature and the second temperature are from about 300° C. to about 600° C.
 73. The process according to claim 72, wherein the first temperature and the second temperature are from about 400° C. to about 550° C.
 74. The process according to claim 48, wherein the first pressure and the second pressure are the same and are from about 1000 bar (10⁵ kPa) to about 10 000 bar (10⁶ kPa).
 75. The process according to claim 74, wherein the first pressure and the second pressure are the same and are from about 1000 bar (10⁵ kPa) to about 5500 bar (5.5×10⁵ kPa).
 76. The process according to claim 75, wherein the first pressure and the second pressure are the same and are from about 1500 bar (1.5×10⁵ kPa) to about 3000 bar (3×10⁵ kPa).
 77. The process according to claim 48, wherein step (iv) is conducted so that the crystallization selectively takes place on the crystallization seed.
 78. A process for preparing a gallium-containing nitride crystal comprising the steps of: (i) providing a gallium-containing feedstock comprising at least two different components, an alkali metal-containing component, at least one crystallization seed and a nitrogen-containing solvent in a container having a dissolution zone and a crystallization zone, whereby the gallium-containing feedstock is provided in the dissolution zone and the at least one crystallization seed is provided in the crystallization zone; (ii) subsequently bringing the nitrogen-containing solvent into a supercritical state; (iii) subsequently partially dissolving the gallium-containing feedstock at a dissolution temperature and at a dissolution pressure in the dissolution zone, whereby a first component of the gallium-containing feedstock is substantially completely dissolved and a second component of the gallium-containing feedstock as well as the crystallization seed(s) remain substantially undissolved so that an undersaturated solution with respect to gallium-containing nitride is obtained; (iv) subsequently setting the conditions in the crystallization zone at a second temperature and at a second pressure so that over-saturation with respect to gallium-containing nitride is obtained and crystallization of gallium-containing nitride occurs on the at least one crystallization seed and setting the conditions in the dissolution zone at a first temperature and at a first pressure so that the second component of the gallium-containing feedstock is dissolved; wherein the second temperature is higher than the first temperature.
 79. The process according to claim 78, wherein the first component of the gallium-containing feedstock is metallic gallium and the second component of the gallium-containing feedstock is gallium nitride.
 80. The process according to claim 78, wherein the crystallization is conducted so that it selectively takes place on the crystallization seed.
 81. The process according to claim 78, wherein the first temperature and the first pressure in the dissolution zone and the second temperature and the second pressure in the crystallization zone are selected so that the concentration of gallium in the over-saturated solution remains substantially the same during crystallization.
 82. The process according to claim 78, wherein the container comprises at least one baffle between the dissolution zone and the crystallization zone.
 83. The process according to claim 82, wherein the at least one baffle has a central opening, circumferential openings or a combination thereof. 